Preparation of a sulfomethylated bisphenol-formaldehyde composition for treating wool



United States Patent ice $293214 Patented Dec. 20, 1966 animal hair fiber products shrink-proof. In addition, We 3,293,214 are not aware of [any successful method for shrink-proof- PREPARATION OF A SULFGMETHYLATED ing wool involving incorporation of a substantive (to BISPHENOL-FORMALDEHYDE COMPOSI- TION FOR TREATEN G WOOL James F. Feeman, Wyomissing, Pa., assignor to Crompton wool) water-soluble condensation product directly in the 5 dye bath or in the laundry wash liquor. 'It seems de- & Knowles Corporation, Worcester Mass. 2 corporw sirable to be able to dye, launder, or otherwise Wet proction of Massachusetts ess woolens in a manner similar to that used presently No Drawing. Filed May 15,1962,Ser.No. 194,993 for cottons, v and synthetics, without the usual 1 Claim. (Cl. 260-49) felting which has heretofore accompanied such wet treatments of wool. The possibility of using a Water-soluble Thi i ti relates t th d d compositions material which is compatible with usual anionic deterfor reducing felting and shrinking of wool and other gents (including Soaps Synthetic Surfactants), and animal hair fibers and to the novel shrink resistant animal Whioh has no deleterious Slde elleot's, directly in the Wash hair fiber products so-produced. Other aspects of this Y hath so h to inhlhlt felting l highly desirable invention are concerned With new techniques for roadju P'feVlous methods of Shrinkage '30111101, and

ducing sulfomethylated condensation products of bisoffers the P p to the Consumer or finisher of being phenols and aldehydes and to the products so-produced. Bible to y of launder finished garments, rather than Felting shrinkage of animal fiber textiles during wet having t depend oI1 a questionable Prior treatment of mechanical processes such as dyeing and laundering has the y fabric. long been a major disadvantage of wool and other ani- I have now vfound that felting Shrinkage of animal mal hair fibers. Without some non-felting or shrinkhair fiber Products and pelt'loularly Wool Y and Y resist treatment, the wool material becomes so dense pro s may e C ntrolled by Wet processing wool in and compact that reduction in area causes it to be unaqueous Solutions Which oontain a Wat r lu le c nusable. Furthermore, the compacted nature of the felted dehsatloh Product having the Probable strllothfei (Structure I) I 1'1 R2 R2 OH HO OH (1 on o R5 a L R5 R1 lm l material i u h that th e i lo of elasticity f the wherein R represents the same or difierent low molecular fabric and the material is difficult to penetrate or clean. W g yl g p -e, those ving from one tofour Currently, it is thought that certain directional fri carbons), R represents the same or different substituents t-ion properties of the fibers, in addition to the ability Selected from the g p and a, m ihtegel to stretch and to recover from stretching, are the primary from 1 to 6, and X represents the Substitution n causes of the felting which occurs when a woolen fabric 40 leverage of from 1 to 2 sulfomethyl groups for each f is ubje ted to repeated t e i th t tbenzene nuclei in the total structure. Where alicyclic A considerable amount of research work in the past ketoIleS Such as oyelo'hexahohe are p y in forming has produced a great variety of methods and techniques the Precursors of these Condensation Products, the 1 aimed at solving the problem. These methods have been groups in the based on various reactions which modify the surface of the wool fiber, alter the elastic properties of the fiber, or act by a combination of these mechanisms. Chemical treatments have involved chlorination, oxidation, reduction, alkaline hydrolysis, enzyme degradation, resin application, and polymerization on or in the fiber. Certain of these treatments are degradatiwe and therefore require careful control to prevent excessive damage to the fibers. Others require special equipment, solvents, expensive reagents, .are hazardous to use, etc. The additive treatments, employing resins and polymers also have certain problems associated with their use. Many of the treatments can only be used on wool fabrics-other Wool forms cannot be effectively processed. Some known treatments cause loss of wool-like hand when too much resin is added on. It has been indicated recently that in the cases of silicones and polyamide-polyepoxides shrinkage control is obtained only at the expense of increased fabric stiffness.

The desired result is attained in many of these methods portion will be linked.

Condensation products having this structure are prepared by a new process which involves condensing two moles of a bis-phenol (compounds produced by reacting a monohydric phenol which is unsubstituted in at least two of the ortho and para positions with an ali- 55 phatic or alicyclic ketone under acid conditions) with from about 1.0 to 1.8 moles of formaldehyde in alkaline solution, making the reaction mass strongly acid and heating to complete the condensation to a Water insoluble resinous material, redissolving the resin by addition of alkali, and treating the solution With from about 1 to about 4 moles of formaldehyde-bisulfite adduct in order to introduce sufiicient sulfomethyl groups to impart water solubility to the product.

The process used to produce the condensation products of this invention is thought to proceed by the following y at the expense of Wool q y as shown by welght steps illustnated for a ratio of 2 moles of Bis-phenol A loss, yello i g, harsh hand, increased luster and (the condensation product of two moles of phenol with cr ased durabili y. G n r l y p g, there is as yet one mole of acetone under acidic conditions) with one no completely satisfactory method available for making mole of formaldehyde:

'(2) Acid condensation I 11+ CH CH3 (3) Sulfomet hylation l ggo lzs O N3 (i133 l Ga @tQ a CH:

An essential feature of this new process involves completely dissolving the bis-phenol compound in aqueous alkali (e.g., aqueous sodium hydroxide solution) before the addition of the formaldehyde. This assures uniformity of degree of polymerization of the final product by giving an even distribution of methylol groups in the available reactive ortho-phenolic positions. Upon acidification of the methylolated bis-phenol, methylene groups are formed between deiferent bis-phenol molecules thereby producing condensation products of relatively low degree of polymerization, i.e., having from two to about seven bis-phenol units of structure in each chain. The number of bis-phenol units present will depend on the amounts of formaldehyde and bis-phenol units employed in the reaction mixture.

Where more than one mole of formaldehyde is employed in the alkaline condensation step, additional methylol groups will be introduced in the bis-phenol and thereby provide additional cross-linkable groups enabling condensation products of greater molecular Weight to be formed.

The use of lower amounts of formaldehyde per bisphenol unit (i.e., those nearer the 1:2 ratio) is preferred,

since the polymeric water-insoluble resin formed in the alkaline and acid condensation is less viscous, more readily handled in manufacture, and is redissolved more easily before sulfomethylation. Desired anti-felting properties of the condensation products produced with the lower amounts of formaldehyde are equal to and in some cases superior to those of condensation products having a higher degree of polymerization.

Preferably, the product of the acid condensation should be completely redissolved before addition of the formal dehyde-bisulfite adduct-this assures uniformity and prop er solubility of the final product, by providing even distribution of solubilizing sulfomethyl groups among and along the polymeric chains. Thus good solubility is achieved with a minimum number of sulfomethyl groups thereby assuring maximum effectiveness of the product.

It is preferred to employ sufiicient formaldehyde-bisul-v fite adduct in the sulfomethylation step to assure reasonable solubility of the final product in cold water at cus tomary laundering or dyeing liquor ratios. This level of sulfomethylation is achieved by use of from 1 to 4 moles of adduct for each two moles of original bis-phenol compound. In such cases, all of the adduct does not react, the amount entering into combination will depend on temperature and time of reaction as well as upon the amount of adduct initially present in the reaction mixture. Where the product of the acid condensation is polymerized to a degree that the polymer includes from 2 to 7 bis-phenol units, it is preferred to employ suflicient formaldehyde-bisulfite adduct to introduce an average of from 1 to 2 sulfomethyl groups for each four benzene nuclei in the polymer. Excessive sulfomethylation reduces the anti-felting action of the resins, presumably by lowering the substantivity of the products to wool.

V/here 2 moles of Bis-phenol A are condensed as described above with 1 to 1.8 moles of formaldehyde and thereafter sulfomethylated, the resultant condensation products are believed to have the structure:

OH HO wherein m is an integer from 1 to 6, and X represents the substitution of an average of from 1 to 2 sulfomethyl groups for each four benzene nuclei in the total structure.

Suitable bis-phenols may be produced by acidic condensation of phenol or o-cresol with acetone, methyl ethyl ketone, cyclohexanone and similar low molecular weight ketones. Mixed bis-phenols prepared from phenol-cresol mixtures may also be used as well as mixtures of homogeneous bis-phenols.

The water-soluble resinous condensation products pro duced according to ths disclosure are, when isolated and dried, essentially colorless solids which have good thermal and light stability, i.e., do not yellow or otherwise discolor noticeably. They may be applied to wool and other animal hair fibers (cashmere, alpaca, mohair, etc.) from aqueous baths at pH values of about 1 to about 9. They can be applied alone or in combination with aqueous solutions or baths containing anonic detergents, dyes, builders, buffers, salts, optical brighteners, etc. In such cases, it is preferred to employ concentrations which will give a pick up of the condensation product on the animal hair or wool of the order of 0.5 to 5% by weight.

The dried condensation products of this invention are compatible with anionic detergents and can be conveniently packaged and marketed as a mixture of the dry solids or as a concentrated aqueous solution of the detergent and the condensation product. Builders and buffer salts can also be incorporated in either the wet or dry mixes.

Although the condensation products of this invention can be applied at pHs ranging from about 1 to 9, best results are obtained where the application is made from a wash liquor or dye bath which is slightly on the acid side. Therefore, it is usually desirable to incorporate buffers which will compensate for differences in the pH of the water employed in the wet treatment, and also the acidity of the hair product undergoing treatment. Generally speaking, it is preferred to employ buffers which will give a pH to the treating liquor of from about 5 to 7.

The disclosed products have, in addition to anti-felting action, a marked beneficial effect in the removal of soil from wool fabrics. The mechanism of action of these products in increasing the detergency of certain anionic detergents, e.g., sodium dodecylbenzene sulfonate, is not known, but the eifect is positive.

These two desirable properties of the condensation products of this invention make them of value generally in wet-processing operations such as scouring, bleaching, dyeing, stripping of dye, mothproofing, laundering, etc., on animal hair products and especially on wool.

The following examples will serve to illustrate the invention and in these examples, unless otherwise stated, the parts are expressed as parts by weight and temperatures are expressed on the centigrade scale:

EXAMPLE 1 Bis-phenol A (2,2-bis-(p-hydroxyphenyl)-propane) (456 parts, 2 moles) and 80 parts of sodium hydroxide are dissolved in 1000 parts of water at 60, and 81 parts (1 mole) of 37% formaldehyde solution is added with continuous stirring. The temperature is raised to 90, held there two hours, and then concentrated hydrochloric acid (265 parts) is added. The mixture separates into two phases, and with continued stirring, the mixture is heated for three hours at 95. The pH is 1 to 1.5 during this time. The viscous organic layer is then redissolved completely by the cautious addition of sodium hydroxide (160 parts) as 50% solution. When solution is complete, a solution of formaldehyde-sodium bisulfite adduct (previously prepared from 162 parts (2 moles) of 37% formaldehyde solution, 165 parts of water, and 200 parts of sodium metabisulfite) is added, and the solution is stirred and heated for 18 hours at 95 C. After cooling, the pH of the resultant clear solution is adjusted to 6.0 by addition of 420 parts of concentrated hydrochloric acid, 200 parts of sodium chloride is added, and the precipitated solid is filtered and dried, giving 710 parts of colorless solid which is readily soluble in cold water to yield a clear solution.

Table I, which follows, lists Examples 2 to 21 wherein are shown additional representative methods of proceeding to yield products of the disclosed type, all having properties which make them useful for the purposes previously described in this disclosure. Additional variations in ratio of reactants will be obvious to those skilled in the art, and these examples are intended to be only representative rather than all-inclusive.

Table I Formalde- Bis-phenol Formalde- NaOH hyde- Ex. No. A used hyde used used for bisulfite (moles) (moles) resolution adduct (parts) used (moles) neutralized, salted, if desired to precipitate the product before drying, and dried conventionally or spray dried.

EXAMPLE 22 2,2 bis (4 hydroxy 3 methylphenyl) propane (102.4parts, 0.4 mole) (prepared by condensation of ocresol with acetone under acidic conditions) is dissolved at 70 in 250 parts of water containing 32 parts of sodium hydroxide. To this solution is added with continuous stirring 16.2 parts of 37% formaldehyde solution, and the temperature is held at for three hours. Then 125 parts of concentrated aqueous hydrochloric acid is added and the temperature held at for two hours. The viscous precipitated resin is then redissolved by addition of 40 parts of sodium hydroxide as 50% solution. After all is in solution, a solution of 0.4 mole of formaldehydebisulfite adduct (prepared from 32.4 parts of 37% formaldehyde solution, 40 parts of water and 40 parts of sodi um metabisulfite) is added. Following an 18 hour period of heating and stirring at 95, the resultant solution is cooled, adjusted to pH 6 with hydrochloric acid, salted with 30 parts of sodium chloride, filtered and dried giving 157 parts of a colorless water-soluble powder.

EXAMPLE 23 A laundering bath is prepared by dissolving 4 parts of the product of Example 1 and 2 parts of sodium dodecylbenzene sulfonate in 2000 parts of water at 120 F. A second laundering bath is prepared by dissolving only 2 parts of sodium dodecylbenzene sulfonate in 2000 parts of water at 120 F.

Into these baths in tumble type washers are entered identical knitted wool garments previously equally soiled (with a synthetic soil of a standard type) and weighing parts each. The garments are washed in conventional fashion for 15 minutes, rinsed, spun dry and dried. The garment washed in the bath containing the product of Example 1 is free of soil and nearly free of felting shrinkage. The garment washed in the bath containing only anionic detergent is still soiled and shows signs of felting.

The washing cycles are repeated using fresh baths for each cycle. After six cycles, the garment washed in detergent only is badly felted and no longer usable, while the treated garment is still in good condition.

EXAMPLE 24 1, l-bis-(4-hydroxyphenyl)-cyclohexane (80.4 parts, 0.3 mole) (prepared by acid condensation of cyclohexanone with phenol) is dissolved at 90 in 200 parts of water containing 24 parts of sodium hydroxide. To this solution is added with continuous stirring 12.2 parts of 37% formaldehyde solution, and the temperature is maintained at 90 for three hours. Then 75 parts of concentrated hydrochloric acid is added and the temperature is kept at 90 for three hours.

A 50% aqueous solution of 40 parts of sodium hydroxide is added, and the mixture is heated and stirred until the precipitate has dissolved. A solution of 30 parts of sodium bisulfite and 24.3 parts of 37% formaldehyde in 30 parts of water is added. The reaction mixture is heated for 18 hours at 90, with constant agitation. The product is precipitated by adjusting the pH to 6,. separated, and dried, giving 123 parts of colorless solid having anti-felting properties when applied to wool in similar manner to that described in Example 23.

EXAMPLE 25 (A) Dyeing using the product of Example I .-A loosely knit Wool fabric weighing 380 parts is placed in a dyebath prepared from 2.28 parts of C1. Acid Yellow 40, 0.76 part of Cl. Acid Red 114, 0.76 part of Cl. Acid Blue 78, 15.2 parts of the product of Example 1, 7.6 parts of acetic acid and 9500 parts of water. The fabric is agitated for one hour at 180 F. in the dyebath to eifect exhaustion of the dye from the bath and give a level dyeing on the fabric. It is then rinsed, spun-dry, and dried in a forceddraft air drier at 170 F. The fabric shows no evidence of felting and is dyed a uniform brown shade.

(B) Control dyeing.--An identical loosely knit wool fabric to that dyed in A weighing 380 parts is placed in a dyebath prepared from 2.28 parts of Cl. Acid Yellow 40, 0.76 part of Cl. AcidRed 114, 0.76 part of Cl. Acid Blue 78, 7.6 parts of acetic acid and 9500 parts of water. The fabric is dyed, rinsed and dried under the identical conditions employed in A. The brown dyed fabric is EXAMPLE 26 In Example 1, while otherwise proceeding as described, if the 456 parts of the bis-phenol A is replaced with 484 parts of 2,2-bis(p-hydroxy phenyl)-butane, a water soluble colorless solid is obtained having properties similar to those of the product of Example 1.

I claim:

A process for preparing a water soluble condensation product which comprises dissolving 2,2-bis(4-hydroxyphenyl) propane in aqueous alkali, condensing 2 moles of the solubilized alkaline bis-phenol with from 1 to 1.8 moles of formaldehyde at temperatures up to reflux, strongly acidifying the reaction mass and heating the acidified mixture to temperatures up to reflux to complete the condensation to a water insoluble resinous material, redissolving the resinous material in aqueous alkali, reacting the redissolved resin in the presence of a compound consisting of from about 1 to 4 moles of formaldehyde-bisulfite adduct at temperatures up to reflux to introduce an average of from l to 2 sulfomethyl groups for each four benzene nuclei in the total structure, precipitating the water soluble condensation product by acidifying and salting the reaction mass and then recovering the precipitated condensation product.

References Cited by the Examiner UNITED STATES PATENTS 2,174,287 9/1939 Guthke 260-49 2,519,978 8/1950 Press 8127.6 2,522,569 9/1950 Day 260-49 2,694,051 11/1954 Black 894.24 2,931,694 4/1960 Wirth 8-65 2,953,597 9/1960 Gedeon et a1 8-94.24 3,029,212 4/ 1962 Lipowski 894.24

WILLIAM H. SHORT, Primary Examiner.

NORMAN G. TORCHIN, Examiner.

J. CANNON, J. C. MARTIN, Assistant Examiners. 

